New non-ionic surface-active agents derived from fatty chain diols and method of preparing same

ABSTRACT

Non-ionic surface-active agents having the formula:   o IN WHICH R is alkyl, alkenyl, alkoxyalkyl and alkaryloxyalkyl, having 8 to 22 carbon atoms, X represents a CH2OH or CH2O-CH2-CHOH-CH2OH group, p and q each independently represent a number between 0 and 10 inclusive with the proviso that the sum of p and q is between 1 and 10 inclusive, in which the radical   INCLUDES WITHIN ITS SCOPE   AND   WHEREIN X is as defined above, are disclosed. The methods for preparing said surface-active agents comprising the step of polycondensing n molecules of glycerol epihalohydrin or allylglycidylether with an Alpha -diol having the formula   HYDROXYLATING THE RESULTING CONDENSATE AND SUBJECTING THE RESULTING HYDROXYLATED PRODUCT TO ETHANOLYSIS.

United States Patent 1191 Kalopissis et al.

1*Apr. 29, 1975 [73] Assignee: Societe Anonyme dite: LOreal, Paris,France 1 Notice: The portion of the term of this patent subsequent toJan. 2, 1990,

has been disclaimed.

[22} Filed: Aug. 9, 1972 121] App]. No.: 279,050

Related [15. Application Data [63] Continuation-impart of Scr. No.(152,005, July 10,

1967. abandoned.

[30] Foreign Application Priority Data July 12, 1966 Luxembourg 51542[52] US. Cl. 252/173; 252/89; 252/156; 252/351; 252/547; 252/548;252/D1G. l [51] Int. Cl. ..Clld 7/26;Cl1d 7/06 [58] Field of Search252/117, 156, DIG. 1, 351, 252/547, 548, 173, 89

156] References Cited UNITED STATES PATENTS 3.427.248 2/1969 Lambcrti eta1. 252/117 3.578.719 5/1971 Kalopissis et al 260/613 B X 3.708.3642/1973 Kalopissis et a1. 252/156 Primary Examiner-Leland A. SebastianAuurney, Agtfll, or FirmCushman, Darby & Cushman [57] ABSTRACT Non-ionicsurface-active agents having the formula:

in which R is alkyl, alkenyl. alkoxyalkyl and alkaryloxyalkyl, having 8to 22 carbon atoms, X repre' sents a CH OH or CH OCH CHOHCH OH group, pand q each independently represent a number between 0 and 10 inclusivewith the proviso that the sum ofp and q is between 1 and 10 inclusive,in which the radical wherein X is as defined above. are disclosed. Themethods for preparing said surface-active agents comprising the step ofpolycondensing n molecules of glycerol epihalohydrin orallylglycidylether with an a-diol having the formula 1i CH CH O11hydroxylating the resulting condensate and subjecting the resultinghydroxylated product to ethanolysis.

2 Claims, No Drawings NEW NON-IONIC SURFACE-ACTIVE AGENTS DERIVED FROMFATTY CHAIN DIOLS AND METHOD OF PREPARING SAME This application is acontinuation-in-part of application Ser. No. 652,005 filed July 10,1967, abandoned in favor of continuation-in-part application Ser. No.52,740, filed July 6, l970, now US. Pat. No. 3,708,364.

There are a large number of non-ionic surface-active agents available,the composition and properties of which are quite varied. However, noneof these known agents made from currently available raw materials haveall of the characteristics required for a considerable number ofapplications.

Thus, for example, in the case of ethylene oxide derivatives an increasein the cloud point to lC or more results in a very marked decrease intheir effec tiveness wetting agents or detergents.

Polyhydroxylated non-ionic surface-active agents are also well known.These surface-active agents are usually prepared by reacting alipophilic compound with hydrosoluble polyols or sugars. This processproduces mixtures of constituents having one or more lipophilic chainsper molecule which must be subjected to onerous purifying steps whenthese products are to be used for purposes which require completesolubility in wa ter.

By introducing hydrophilic substitue nts on the hydrocarbon chain oradding ethylene oxide to the free hydroxyl groups, the solubility ofthese compounds in water may be improved.

But because they consistently comprise an ester bond between thelipophilic chain and the hydrophilic component, the resulting compoundsare easily hydrolysed in an alkaline medium.

The purpose of the present invention is to provide non-ionicsurface-active agents which are both stable and soluble in water at hightemperatures even in the presence of electrolytes and which agents havevery valuable surface-active properties.

More particularly, one embodiment of the present invention is directedto a method for preparing nonionic surface-active agents having theformula:

it CPLCY.

wherein R has the meaning given above, n molecules of glycerolepihalohydrin where n is equal to the sum of p and q defined above, at atemperature ranging from 25 [60C in the presence of an acid catalystselected from the group consisting of boron fluoride, stannic chlorideand antimony pentachloride,

2. hydroxylating the resulting condensate from l l in the presence of analkaline carboxylic acid salt as an hydroxylating agent at a temperaturebetween 230C, and

3. subjecting the resulting hydroxylated product from step (2) toethanolysis thereby producing said nonionic surface-active agent.

Another embodiment of the present invention relates to a method forpreparing non-ionic surface-active agents having the formula:

l? Cli-Cll wherein R is selected from the group consisting of al kyl,alkenyl, alkoxyalkyl, alkaryloxyalkyl, having 8 22 carbon atoms, X is CHOCH CHOHCH OH, p and q each independently represent a number between 0and 10 inclusive, with the proviso that the sum of p and q is between 1and 10 inclusive, the steps comprising 1. condensing on an a-diol havingthe formula:

wherein R has the meaning given above, n molecules of allyl glycidylether where n is equal to the sum ofp and q defined above, at atemperature ranging from 25 C in the presence of (l an acid catalystselected from the group consisting of boron fluoride, stannic chlorideand antimony pentachloride, or (2) a basic catalyst such astriethylamine,

2. hydroxylating the resulting condensate from step l in the presence ofan organic per acid as an hydroxylating agent at a temperature between20 80C, and

3. subjecting the resulting hydroxylated product from step (2) above toethanolysis thereby producing said non-ionic surface-active agent.

Yet another embodiment of the present invention is the provision ofnon-ionic surface-active agents having the formula:

1 cit-0:1,. L 0, ii 0 -l? c. I 07 n 0 l 3 l t wherein X is as definedabove.

Still another embodiment of the present invention is the provision ofnon-ionic surface-active agents having the formula:

R li-Cli C ll OX H wherein R is selected from the group consisting of alkyl, alkenyl, alkoxyalkyl or alkylaryloxyalkyl, having 8 22 carbonatoms, X is CH O CH CHOHCH- 0H, p and q each independently represent anumber between 0 and 10 inclusive, with the proviso that the sum of pand q is between 1 and I0 inclusive.

In the production of the non-ionic surface-active agents in accordancewith the process of the present invention, after completion of thecondensation step and before hydroxylation, intermediate compounds ofthe following formula are produced.

wherein R, p and (1 have the meaning given above and Y represents CH Zor CH OCH -CH=CH wherein Z is a halogen.

During the condensation reaction which comprises the first step of theprocess according to the invention, a mixture of compounds, all of whichrespond to the formula for said intermediate compounds described aboveis formed. For each of these the total number of [C H O Y] groupsattached to the two alcohol functions of the a-diol employed may begreater or less than the statistical average value of the number ofmolecules of allyl-glycidyl-ether or glycerol epihalohydrin used permolecule of a-diol. The process according to the invention thus makes itpossible to obtain a mixture of compounds in which the importance of thehydrophilic chains is dependent on the value of the sum (p-l q) of theparameters p and q, the group of values of (pl-q) being statisticallydistributed about an average value corresponding to the number ofmolecules used per molecule of alcohol. But the important fact whichshould be emphasized and which leads to one of the essential advantagesof the process of preparation according to the invention is that thisprocess leads to the formation of compounds having a single lipophilicchain for each hydrophilic chain The result is that the These a-diolsmay be prepared by hydroxylation, in accordance with known processes,from long-chain a-olefins, in pure form or in commercial mixtures.

The process according to the invention is also applicable to hydroxylcompounds having mixed functions such as the alkoxy-alkanediols or thealkyl-aryloxyalkanediols. These include the glycerol monocthers such asthe lauryl-, tetradecyl-hexadecyl-, octadecyl-, octadecenyl-,octylphenyl-, and nonylphenylmonoethers of glycerol.

In accordance with the process of the present invention the condensationreaction may be carried out in the presence of an acid catalyst such asboron fluoride, stannic chloride or antimony pentachloride, or whenusing allyl glycidylether, in the presence ofa base catalyst such astriethylamine. This reaction is carried out at a temperature between 25Cand l60C and preferably between 40 and l00C.

When glycerol epihalohydrin is reacted during the condensation reaction,the hydroxylation reaction which comprises the second step of theprocess is based on the reaction of the halogenated derivative, obtainedduring the condensation reaction, with an alkaline carboxylic acid salt,preferably in a solvent which insures the miscibility of the reagentsand the ready separation of the mineral halide formed. Thishydroxylation reaction takes place between [30C and 230C, and preferablyabout 180C.

With respect to this hydroxylation step it should be noted that thealkaline salt of carboxylic acid employed may advantageously be anacetate, in stoichiometric proportions, or slightly in excess thereof,i.e., about l0 15 percent in excess, relative to the halogenatedcompounds which participate in the reaction.

When allyl glycidyl ether is reacted during the condensation reaction,hydroxylation is preferably effected by means of an organic peracidformed in situ from hydrogen peroxide and an organic acid such as, forexample, acetic acid or formic acid. This reaction is carried outbetween 20C and C and preferably between 30C and 50C.

After separation of the mineral halide resulting from the hydroxylationreaction, the partially esterified polyhydroxylated polyether issubjected to alcoholysis by means of acetic acid, preferably with theair of absolute ethyl alcohol, in the presence of an alcoholysiscatalyst at ambient temperature,

The resulting nonionic surface-active agents of this invention may beused as wetting agents, detergents, or foaming agents. They haveparticularly valuable properties with respect to solubility. They arecompatible with aqueous concentrated sodium hydroxide solutions (forexample up to 40 percent by weight), and for this reason have manypossible industrial applications, particularly in cleaning, metaldescaling, and degreasing operations carried out at high temperaturesand in the presence of electrolytes.

It should also be noted that, as compared with nonionic surface-activeagents derived from ethylene oxide and comprising an analagouslipophilic chain, the compounds according to the invention have theadvantage of being very effective wetting agents even though they remainsoluble in water at high temperatures, even in the presence ofelectrolytes.

The following table gives several wetting times at 25C measuredaccording to the Canvas Disk" method described in .l. C. Harrispublication Deter- Coivnound subjected to tests 23 a. laur'yl radicalwith n R II II with p+o 3.5 alkyl radical carbon atoms comprisi n5 9 c.-1 o(cn o1.) 3 1:

with n+6; 3.5

Another object of the invention is to provide a cleansing, a shampoo ora detergent composition essentially characterized by the fact that itcontains the surface-active agent of the present invention.

The detergent composition according to the present invention ispreferably an aqueous solution or paste containing about l to 50 percentof the surface-active agent of this invention, said composition having apH of about 3 9. This composition may also include products or additivescustomarily used in such industrial products, as for example, thickeningagents, sequestrants, anti-settling agents, etc, mineral oil and ionicor non-ionic surface-active agents other than those of this invention.

In order that the invention may be better understood, the followingillustrative examples are given and unless otherwise specified all partsand percentages are by weight.

EXAMPLE l Preparation of the non-ionic surfaceactive agent of theformula:

wherein the sum (p-l-q) has a statistical average value The startingmaterial is l,2-tetradecane diol, prepared by hydroxylation ofl-tetradecane by the method described by Swern in Organic Reactions,Vol. VII at page 399. The l-tetradecene used to prepare the 1,2-tetradecanediol is a commercial product sold by the Gulf OilCorporation.

First phase: Condensation reaction 0.20 ml of an acetic compositioncontaining 36 percent BF is added to 34.5 g of distilled a-diol having aClout. Po nt. le ltv n 1' In titTJ- rife; m t iro. tilled water water(101i m ll 2101 more than 81C more than 100C 5 minutes more more secondsthan than 97- 5C 97. 5C

more more 2 1 second? than than 98C 98C boiling point of C at a pressureof 1 mm of mercury, which was melted at the moment of use. 48.5 g ofglycerol epichlorohydrin are added, while the mixture is agitated. Thetemperature is kept between 40 and 50C and the reaction lasts for 45minutes.

The result is a polychlorinated polyether.

Second phase: Hydroxylation reaction 72 g of the product obtained inthis manner are treated with 45 g of potassium acetate, l20 gdipropylene glycol being used as solvent. The hydroxylation reaction iscarried out at C and lasts 3 hours. The potassium chloride thus obtainedis filtered from the reaction mass.

The dipropylene glycol solvent is then evaporated and the resultingresidue is subjected to alcoholysis by adding to the residue 350 ml ofabsolute ethyl alcohol together with an alcoholysis catalyst consistingof 2.5 g of a solution in methanol containing 25 weight percent ofsodium methylate. The resulting alcoholysis reaction mixture is leftstanding overnight at ambient temperature. Thereafter the alcohol andresulting ethyl acetate are removed thus providing the above definednon-ionic surface-active agent.

This non-ionic surface-active agent is in the form of a very viscousyellow syrup which is easily dissolved in water. lts cloud point,determined for a 0.5 percent so lution, is above 98C both in distilledwater and in salt water containing 10 percent sodium chloride. Thisnonionic surface-active agent when mixed with a 30 percent by weightaqueous solution of sodium hydroxide, gives a paste suitable fordescaling metal.

EXAMPLE 2 Preparation of the non-ionic surface-active agent of theformula:

l; op ng (LnPHi wherein R represents linear alkyl chains having 9 to 13carbon atoms, the sum Uri-q) having a statistical aver age value of 3.5.

First phase: Condensation reaction The starting material is an adiolobtained by hydroxylation in accordance with the method described inSwern's Organic Reactions," Vol. VII, at page 399, beginning with amixture of straight chain olefins comprising l 1 to carbon atoms andsold commercially under the trademark Chevron Alpha Olefins, by theCronite Company.

025 ml of an acetic composition containing 36 percent of BF is added to44 g of an a-diol obtained in this manner, which has first beendistilled at between 140 and 153C under a pressure of 1 mm of mercuryand melted at the moment of use. 65 g of glycerol epichlorohydrin arethen poured in, The reaction lasts 50 minutes. during which thetemperature is kept between 40 and 50C.

This yields a polychlorinated polyether.

Second phase: Hydroxylation reaction The polychlorinated ether obtainedduring the first step is hydroxylated with potassium acetate, usingdipropylene glycol as a solvent and maintaining the temperature at 180Cfor 3 hours. The resulting potassium chloride is filtered, the solventis evaporated, and after subsequent ethanolysis conducted in a manneressentially as outlined in Example 1, a non-ionic surfaceactive agent ofthe formula given at the beginning of this Example is obtained. Thisnon-ionic surface active agent is in the form of a yellowish syrup, thecloud point of which in 0.5 percent solution as described above, hasalready been given. This product is compatible with aqueous solutionscontaining 30 percent by weight of sodium hydroxide. At a concentrationof 1 percent in a 10 percent sodium hydroxide solution, the productretains its wetting properties (wetting time at C 140 seconds).

EXAMPLE 3 Preparation of the non-ionic surface-active agent of theformula:

C 1-1 5(lI1-l-CH 0 --EC ll3 wherein the sum (p+q) has a statisticalaverage value of 1.75.

First phase: Condensation reaction The starting material used is 1,2tetra-decanediol prepared by hydroxylizing l-tetradecene by the methoddescribed in Swerns Organic Reactions. Vol. VII. at page 399. Thel-tetradecene used to prepare the l,2-tetradecanediol is soldcommercially by the Gulf Oil Corporation. 0.1 ml of an aceticcomposition containing 36 percent BF is added, while stirring, to 27.5 gof 1,2-tetradecanediol distilled at 160C under a pressure of 1 mm ofmercury, and melted at the moment of use. 24 g of allyl glycidyl etherare then added drop by drop while maintaining the temperature at about60C. The reaction lasts for about 35 minutes.

Second phase: Hydroxylation reaction 48 g of the product thus obtainedare dissolved in 55 g of 98 percent formic acid and 25 ml of hydrogenperoxide at 116 volumes are then added progressively. After a reactionlasting for 27 hours at 40C those peroxides formed are destroyed withsodium sulfite and the formic acid is evaporated.

This is followed by ethanolysis essentially as described in Example 1,which results in a colorless semisolid nonionic surface-active agent asdefined above, which dissolves readily in water and is a good foamingagent. In an 0.5 percent solution. it has a cloud point above 97C bothin distilled water and in salt water containing 10 percent sodiumchloride.

EXAMPLE 4 Preparation of the non-ionic surface-active agent of theformula:

P Ci'wfl 0 l1. 0 (m on) +11 wherein R is an alkyl radical containing 13to 18 carbon atoms and the sum (p+q) has a statistical average value of6.

First phase: Condensation reaction The starting material used is amixture of a-diols obtained by hydroxylizing with hydrogen peroxide, ina medium containing formic acid and ethyl formate, a mixture of olefinscomprising 15 to 20 carbon atoms and sold commercially under thetrademark Chevron Alpha Olefins" by the Oronite Company.

0.40 ml of an acetic composition containing 36 percent BF is added to 73g of a-diols recrystallized in petroleum ether and melted at the momentof use. 139 g of glycerol epichlorohydrin are then added drop by drop.The operation takes 45 minutes and the temperature is kept between 60and C.

The reaction is terminated by adding an additional 0.1 m1 of the aceticcomposition containing boron fluoride, while heating in a boiling waterbath for about an hour.

This results in a liquid polychlorinated polyether which is yellow incolor.

0 cu -OCH C11011-C11 OH H Second step: Hydroxylation reaction 123.5 g ofanhydrous potassium acetate and 0.9 g of potassium borohydride aredissolved in 300 g of dipropylene glycol. The resulting solution isheated to 180C and 177.5 g of the polychlorinated polyether prepared inthe first step is added thereto. After a reaction lasting 3 hours at Cthe potassium chloride formed is filtered and the solvent is evaporated.The product is de-acetylated by ethanolysis in accordance with theprocedures set forth in Example 1.

The resulting non-ionic surface-active agent as defined above is in theform of a paste which is soluble in water. The cloud point in the caseof 0.5 percent solutions, both in distilled water and in salt watercontaining 10 percent of sodium chloride, is about 100C. This -{c,u cuOCH -Cll0ll-Cll on ll 0 3 2 2 2 )3 non-ionic surface-active agent issoluble in a 40 percent 5 sodium hydroxide solution.

Several examples of useful compositions including the non-ionicsurface-active agent of this invention are bel w1 given 0 [0 EXAMPLE 5 Agel is prepared in the following manner: To grams of the non-ionicsurface-active agent of the formula:

Pl Clll Cll O--{C l O (Cll Oli) ]pl O-E- C ll 0 (Cll Oil) +ll wherein Rrepresents linear alkyl containing 9 to 13 carbon atoms and wherein thesum (p-i-q) has a statistical average value of 3.5, there are added l0grams of a percent soda lye solution. After homogenization, b a clearyellow gel is obtained. This composition may be used to clean householdovens and can be applied by means of a damp cloth.

EXAMPLE 6 A gel is prepared by mixing l0 grams of a 30 percent soda lyesolution with ID grams of a non-ionic surfaceactive agent of theformula:

(the sum (p+i having a statistical average value of L75] l0 g Copradiethanolamide l g Polyethylene glycol (molecular weight about5.000.000) 0.l g

- Water, qsp. l00 g.

x l R-CHCH2-O E C2H30 ila wherein R is selected from the groupconsisting of alkyl, alkenyl, alkoxyalkyl or alkylaryloxyalkyl, having 822 carbon atoms, X is CH OH, p and q each independently represent anumber between 0 and 10 inclusive, with the proviso that the sum ofp andq is between l and 10 inclusive, and that q is other than zero when v'l1' 12 1 CH 3 Ti 3 (F 5 R has 8 l2 carbon atoms and p is one.

(3 h 9 (CH 2. A composition consisting essentially of an aqueous 3 2 0solution containing surface-active amounts of a nonionic surface-activeagent of the formula:

wherein the sum (p-l-q) has a statistical value of 3.5. 40 X Afterhomogenization, a clear yellow gel is obtained l which can be used toclean household ovens, the same R-CH-CH 0 C H 0 3- H 2 2 3 p beingapplied thereto with a damp cloth.

X EXAMPLE 7 I A hair shampoo composition is prepared as follows: 0 E ZIB q C ll Cll-Cl'1 OP C H O Cll OCl -CilOllCll OH H 12 25 I 2 2 3 2 2 2%I J O C H 0 Oil OCH CHOHCH OH ll (the sum (p+q) having a statisticalaverage value of 1.75) [0 g cetyl-trimethyl ammonium bromide 3 g 4lactic acid qsp. pH

- water, q.s.p. I00 g EXAMPLE 8 A hair shampoo composition is preparedas follows:

wherein R is selected from the group consisting of alkyl, alkenyl,alkoxyalkyl or alkylaryloxyalkyl, having 8 22 carbon atoms, X is -CH OCHCH OH-CH OH,

p and q each independently represent a number between 0 and 10inclusive, with the proviso that the sum ofp and q is between I and l0inclusive.

1. A COMPOSITION, CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTIONCONTAINING SURFACE ACTIVE AMOUNTS OF A NON-IONIC SURFACEACTIVE AGENTHAVING THE FORMULA:
 2. A composition consisting essentially of anaqueous solution containing surface-active amounts of a non-ionicsurface-active agent of the formula: